Crop protection products

ABSTRACT

Plant-protecting mixtures of active ingredients having a synergistically increased action, wherein component I is a compound having a plant-immunizing action of the formula I ##STR1## in which Z is CN, COOH or a salt thereof, CO--OC 1  -C 4  alkyl or CO--SC 1  -C 4  alkyl; 
     and wherein component II is a compound selected from the group consisting of propiconazole, difenoconazole, penconazole, fenpropimorph, fenpropidine, cyprodinil, metalaxyl, R-metalaxyl and pyroquilon.

This application is a 371 of PCT/EP96/00096, filed Aug. 11, 1996.

The present invention relates to novel crop-protecting mixtures ofactive ingredients having a synergistically increased action, thismixture comprising at least one compound having a plant-immunizingaction and at least one compound having a microbicidal action, and tomethods for using such mixtures in crop protection, in particular forcontrolling and preventing the incidence of disease.

Component I is a plant-immunizing compound of the formula I ##STR2## inwhich Z is CN, COOH or a salt thereof, CO--OC₁ -C₄ alkyl or CO--SC₁ -C₄alkyl;

component II is a compound selected from the group consisting of

A) 1-2-(2,4dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl!-1H-1,2,4-triazole,("propiconazole"), (reference: GB-1 522 657);

B) 1-{2-2-chloro-4-(4-chlorophenoxy)phenyl!-4-methyl-1,3-dioxolan-2-ylmethyl}-1H-1,2,4-triazole,("difenoconazole"), (reference: GB-2 098 607);

C) 1- 2-(2,4dichlorophenyl)pentyl-1H-1,2,4-triazole, ("penconazole"),(reference: GB-1 589 852);

D) cis-4- 3-(4tert-butylphenyl)-2-methylpropyl!-2,6-dimethylmorpholine,("fenpropimorph"), (reference: DE 2 752 135);

E) 1- 3-(4-tert-butylphenyl)-2-methylpropyl!piperidine, ("fenpropidin"),(reference: DE 2 752 135);

F) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine ("cyprodinil")(reference: EP-A-310 550);

G) (RS)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester("metalaxyl"), (reference: GB-1 500 581);

H) (R)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester("R-metalaxyl"), (reference: GB-1 500 581);

J) 1,2,5,6-tetrahydro-4H-pyrrolo 3,2,1-ij!quinolin-4-one ("pyroquilon"),(reference: GB-1 394 373).

The invention also relates to salts and metal complexes of the compoundsI and II

Preferred compounds among those of the formula I are compounds in whichZ is COOH (compound IA) or a salt thereof, CN (compound IB), COOCH₃(compound IC) or COSCH₃ (compound ID).

Preferred salts are alkali metal and alkaline earth metal salts, inparticular Li, Na, K, Mg or Ca salts, furthermore organic salts, inparticular those of salt-forming amines, for example trimethylamine,triethylamine, N,N-dimethylaniline, pyridine, triethanolamine,morpholine.

Very particularly preferred is the compound of the formula I in which Zis CO--SCH₃ (compound ID).

It has been disclosed that compounds of the formula I activate theplant's latent, own defence system against the effects of pathogenicmicrobes and thus are capable of protecting the plant against pathogens(EP-A-313 512). At low rates of application, these compounds are notdirectly active against the harmful organisms, but cause immunization ofthe healthy plant against diseases. The disadvantage of controllingplant diseases using compounds of the formula I is that the action isfrequently insufficient at low rates of application.

Surprisingly, it has now been found that compounds of the formula I,when mixed in certain ratios with one of the conventional microbicidesIIA to IIJ, have a synergistically increased action. Such mixtures aresuitable for controlling plant diseases by, on the one hand,strengthening the plant by activating its own defence system and, on theother hand, additionally controlling the pathogens directly. Incomparison with the conventional methods of controlling plant diseases,unexpectedly low amounts of active ingredients are required. Aparticular advantage of the mixtures according to the invention isfurthermore the fact that the build-up of resistance, of plant diseases,is prevented effectively by the completely different mechanisms ofaction of components I and II. The synergistically increased action ofmixtures of components I and II is shown, for example, by the lowerrates of application, the longer duration of action and the higheroverall yields than was to be expected from the total of the actions ofthe individual components.

The present invention also relates to a method of protecting plantsagainst plant diseases, in particular fungus infestation, by treatingthe plants, parts of plants or their environment with a component I anda component II in any order or simultaneously.

Advantageous mixing ratios of the two active ingredients are I:II=1:30to 10:1, preferably I:II=1:20 to 2:1 and 1:10 to 1:1.

Particularly advantageous mixing ratios are

I:IIA=1:1 to 1:6

I:IIB=1:1 to 1:6

I:IIC=1:1 to 1:5

I:IID=1:1 to 1:10

I:IIE-1:1 to 1:10

I:IIF=1:20 to 1:10

I:IIG=10:1 to 1:10

I:IIH=10:1 to 1:5

I:IIJ=10:1 to 1:10

The mixtures according to the invention of active ingredients I+II havevery advantageous properties for protecting plants against the incidenceof disease. The present mixtures of active ingredients are capable ofcontaining or destroying the microorganisms which occur on plants orparts of plants (fruits, flowers, foliage, stalks, tubers, roots) of avariety of crops of useful plants, and even parts of plants which areformed at a later point in time remain unharmed by such microorganisms.They can also be employed as seed-dressing agents for treatment of plantpropagation material, in particular seed (fruits, tubers, kernels) andnursery plants (for example rice) as a protection against fungalinfections and against soil-borne phytopathogenic fungi. The mixtures ofactive ingredients according to the invention are distinguished byparticularly good toleration by plants and favourable ecologicalproperties.

The mixtures of active ingredients are effective against thephytopathogenic fungi of the following classes: Ascomycetes (for exampleVenturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula);Basidiomycetes (for example the genera Hemilcia, Rhizoctonia, Puccinia);Fungi imperfecti (for example Botrytis, Helminthosporium,Rhynchosporium, Fusarium, Septoria, Cercospora, Altemaria, Pyriculariaand, in particular, Pseudocercosporella herpotrichoides); Oomycetes (forexample Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).

Target crops for the fields of indication disclosed in the presentpublication are, within the scope of the invention, for example thefollowing plant species: cereals (wheat, barley, rye, oats, rice,sorghum and related species); beet (sugar and fodder beet); pomaceousfruit, stone fruit and soft fruit (apples, pears, plums, peaches,almonds, cherries, strawberries, raspberries and blackberries);leguminous plants (beans, lentils, peas, soya beans); oil crops (oilseedrape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa,groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants(cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit,tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots,onions, tomatoes, potatoes, bell peppers); the laurel family (avocado,Cinnamonum, camphor), or plants such as maize, tobacco, nuts, coffee,sugar cane, tea, grapevines, hops, the plantain family and latex plants,and also ornamentals (flowers, shrubs, deciduous trees and conifers).This enumeration is not by way of limitation.

The mixtures of active ingredients according to the invention areparticularly advantageous for the following applications:

I+IIA, I+IIB, I+IID, I+IIE: in cereals, very particularly in wheat andbarley;

I+IIG, I+IIH, very particularly I+IIH: in potatoes, grapevines, lawns,hops, tobacco and vegetables;

I+IIJ: in rice.

The mixtures of active ingredients of the formulae I and II areconventionally used in the form of compositions. The active ingredientsof the formulae I and II can be applied to the area or plant to betreated either simultaneously or in succession on the same day, ifdesired together with other carriers conventionally used in the art offormulation, surfactants or other additives which aid application.

Suitable carriers and additives can be solid or liquid and are thesubstances expediently used in the art of formulation, for examplenatural or regenerated mineral materials, solvents, dispersants, wettingagents, adhesives, thickeners, binders or fertilizers.

A preferred method of applying a mixture of active ingredientscomprising in each case at least one of these active ingredients I andII is application to the aerial parts of the plant, especially thefoliage (foliar application). Number and rates of application depend onthe biological and climatic environment of the pathogen. Alternatively,the active ingredients can reach the plant from the soil or water viathe root system (systemic action) by drenching the locus of the plantwith a liquid preparation (for example in rice growing) or incorporatingthe substances into the soil in solid form, for example in the form ofgranules (soil application). The compounds of the formulae I and II canalso be applied to seed kernels for the purposes of seed treatment(coating), either by soaking the roots or kernels in succession with aliquid preparation of an active ingredient or by coating them with amoist or dry preparation which already comprises the combination. Inaddition, other types of application to plants are possible in specificcases, for example the targeted treatment of buds or fruit-bearing partsof the plant.

The compounds of the combination are employed as pure active ingredientsor, preferably, together with the auxiliaries conventionally used in theart of formulation and are therefore processed in a known manner togive, for example, emulsion concentrates, spreadable pastes,ready-to-spray or ready-to-dilute solutions, dilute emulsions, wettablepowders, soluble powders, dusts, granules, or encapsulations, forexample in polymeric materials. The methods of application, such asspraying, atomizing, dusting, scattering, brushing on or pouring, andthe type of composition are selected to suit the intended aims andprevailing circumstances. Advantageous rates of application of themixture of active ingredients are generally 50 g to 2 kg of a.i./ha, inparticular 100 g to 1000 g of a.i./ha, particularly preferably 150 g to700 g of a.i./ha. For the treatment of seed, the rates of applicationare 0.5 g-1000 g, preferably 5 g-100 g of a.i. per 100 kg of seed.

The formulations are prepared in a known manner, for example byintimately mixing and/or grinding the active ingredients with extenders,for example solvents, solid carriers and, if desired, surface-activecompounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, for example xylene mixtures or substituted naphthalenes,phthalic esters, such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols andglycols and also their ethers and esters, such as ethanol, ethyleneglycol, ethylene glycol monomethyl ether or ethylene glycol monoethylether, ketones, such as cyclohexanone, strongly polar solvents, such asN-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, andfree or epoxidized vegetable oils, such as epoxidized coconut oil orsoya oil; or water.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals, such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly-disperse silica orhighly-disperse absorptive polymers. Suitable particulate adsorptivecarriers for granules are porous types, for example pumice, brick grit,sepiolite or bentonite, and suitable non-sorptive carrier materials are,for example, calcite or sand. Moreover, a large number of pregranulatedmaterials of inorganic or organic nature can be used, such as, inparticular, dolomite or comminuted plant residues.

Depending on the nature of the active ingredients of the formulae I andII to be formulated, suitable surface-active compounds are non-ionic,cationic and/or anionic surfactants having good emulsifying, dispersingand wetting properties. Surfactants are also to be understood as meaningmixtures of surfactants.

Particularly advantageous additives which aid application are,furthermore, natural or synthetic phospholipids from the series of thecephalins and lecithins, for example phosphatidylethanolamine,phosphatidylserine, phosphatidylglycerine, lysolecithin

As a rule, the agrochemical preparations comprise 0.1 to 99%, inparticular 0.1 to 95%, of active ingredients of the formulae I and II,99.9 to 1%, in particular 99.9 to 5%, of a solid or liquid additive and0 to 25%, in particular 0.1 to 25%, of a surfactant.

While concentrates are more preferred as commercially available goods,the end consumer uses, as a rule, dilute compositions.

Such compositions are part of the present invention.

The examples which follow are intended to illustrate the invention,"active ingredient" being to be understood as meaning a mixture ofcompound I and compound II in a certain mixing ratio.

FORMULATION EXAMPLES

    ______________________________________                                        Wettable powders  a)        b)     c)                                         ______________________________________                                        Active ingredient 25%       50%    75%                                         I:II = 1:3 (a), 1:2 (b), 1:1 (c)!                                            Sodium lignosulfonate                                                                           5%         5%    --                                         Sodium laurylsulfate                                                                            3%        --      5%                                        Sodium diisobutylnaphthalene-                                                                   --         6%    10%                                        sulfonate                                                                     Octylphenol polyethylene                                                                        --         2%    --                                         glycol ether                                                                  (7-8 mol of ethylene oxide)                                                   Highly disperse silica                                                                          5%        10%    10%                                        Kaolin            62%       27%    --                                         ______________________________________                                    

The active ingredient is mixed thoroughly with the additives and themixture is ground thoroughly in a suitable mill. This gives wettablepowders which can be diluted with water to give suspensions of anydesired concentration.

    ______________________________________                                        Emulsion concentrate                                                          ______________________________________                                        Active ingredient (I:II = 1:6)                                                                       10%                                                    Octylphenol polyethylene glycol ether                                                                 3%                                                    (4-5 mol of ethylene oxide)                                                   Calcium dodecylbenzenesulfonate                                                                       3%                                                    Castor oil polyglycol ether                                                                           4%                                                    (35 mol of ethylene oxide)                                                    Cyclohexanone          30%                                                    Xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired dilution which can be employed in cropprotection can be prepared from this concentrate by dilution with water.

    ______________________________________                                        Dusts             a)        b)     c)                                         ______________________________________                                        Active ingredient  I:II = 1:4 (a);                                                               5%        6%     4%                                        1:5 (b) and 1:1 (c)                                                           Talc              95%       --     --                                         Kaolin            --        94%    --                                         Rock meal         --        --     96%                                        ______________________________________                                    

Ready-to-use dusts are obtained by mixing the active ingredient with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry seed treatment.

    ______________________________________                                        Extruder granules                                                             ______________________________________                                        Active ingredient (I:II = 2:1)                                                                    15%                                                       Sodium lignosulfonate                                                                              2%                                                       Carboxymethylcellulose                                                                             1%                                                       Kaolin              82%                                                       ______________________________________                                    

The active ingredient is mixed with the additives, ground and moistenedwith water. This mixture is extruded and subsequently dried in a streamof air.

    ______________________________________                                        Coated granules                                                               ______________________________________                                        Active ingredient (I:II = 1:10)                                                                    8%                                                       Polyethylene glycol (MW 200)                                                                       3%                                                       Kaolin               89%                                                      ______________________________________                                         (MW = molecular weight)                                                  

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin which has been moistened with polyethylene glycol. This givesdust-free coated granules.

    ______________________________________                                        Suspension concentrate                                                        ______________________________________                                        Active ingredient (I:II = 1:7)                                                                       40%                                                    Propylene glycol       10%                                                    Nonylphenol polyethylene glycol ether                                                                 6%                                                    (15 mol of ethylene oxide)                                                    Sodium lignosulfonate  10%                                                    Carboxymethylcellulose  1%                                                    Silicone oil            1%                                                    (in the form of a 75% aqueous emulsion)                                       Water                  32%                                                    ______________________________________                                    

The finely ground active ingredient is mixed intimately with theadditives. This gives a suspension concentrate from which suspensions ofany desired dilution can be prepared by dilution with water. Suchdilutions can be used for treating live plants and plant propagationmaterial by means of spraying, pouring-on or immersion and forprotecting them against microbial infection.

BIOLOGICAL EXAMPLES

A synergistic effect is present if the action of the combination ofactive ingredients exceeds the total of the actions of the individualcomponents.

The expected action E for a given combination of active ingredients canbe described by the so-called COLBY formula and can be calculated asfollows (COLBY, S. R. "Calculating synergistic and antagonisticresponses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per litre of spray mixture

X=% action caused by active ingredient I at a rate of application of pppm of active ingredient

Y=% action caused by active ingredient II at a rate of q ppm of activeingredient

E=expected action of active ingredients I+II at a rate of application ofp+q ppm of active ingredient (additive action),

then Colby's formula reads ##EQU1##

If the actually observed action (O) exceeds the expected action (E), theaction of the combination is superadditive, i.e. there is a synergisticeffect. O/E=factory of synergism (FS). In the examples which follow, theinfestation of the untreated plant is considered 100%, which correspondsto an action of 0%.

A) Examples in which

Component I: Compound ID (thiomethyl benzothiadiazole-7-carboxylate)

Component II: Compound IIA (propiconazole)

EXAMPLE A1

Action against Puccinia recondita in wheat

7-day-old wheat plants are sprayed to drip point with a spray mixtureprepared from a formulated active ingredient, or combination of activeingredients. After 4 days, the treated plants are infected with aconidia suspension of the fungus, and the treated plants aresubsequently incubated for 2 days at a relative atmospheric humidity of90-100% and 20° C. 10 days post-infection, the fungus infestation isassessed. The following results are obtained:

    ______________________________________                                                                  % action                                            Exp.  mg of a.i. per liter                                                                              found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIA I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     100     --            51                                                2             5             10                                                3     100     5        20:1 79      56     1.4                                ______________________________________                                    

EXAMPLE A2

Action against Erysiphe graminis in wheat in the open (experimentalsite: Les Barges, Dalais, Switzerland

In a field trial (10 m²), winter wheat cv. "Bernina" in the growth phaseis sprayed with a spay mixture prepared with a wettable powder of theactive ingredient. Infection is naturally. 10 days post-infection, thefungus infestation is assessed. The following results are obtained:

    ______________________________________                                                                  % action                                            Exp.  g of a.i. per ha    found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIA I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     5       --            29                                                2     --       50            2                                                3     --      100           31                                                4     5        50      1:10 49      32     1.5                                5     5       100      1:20 59      51     1.2                                ______________________________________                                    

EXAMPLE A3

Action against Mycosphaerella fijiensis in bananas (experimental site:Ombu Farm, Prov. Limon, Costa Rica)

40 banana plants in a 300 m² plot are sprayed at 17-19 day intervalswith a spray mixture prepared with the wettable powder of the activeingredient; in total 6 times. Infection is naturally. For evaluation,the leaf area infested with fungus is measured. The following resultsare obtained:

    ______________________________________                                                                  % action                                            Exp.  g of a.i. per ha    found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIA I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     50      --            19                                                2     --      50            26                                                3     50      50       1:1  46      40     1.15                               ______________________________________                                    

Similarly good results are obtained using mixtures of one of thecompounds IA, IB or IC with the compound IIa.

B) Examples in which

Component I: Compound ID (thiomethyl benzothiadiazole-7-carboxylate)

Component II: Compound IIF (cyprodinil)

EXAMPLE B1

Action against Erysiphe graminis in wheat in the open (experimentalsite: Whittlesford, England)

In a field trial (10 m²), winter wheat cv. "Kanzler" in growth phase31-32 is sprayed with a spray mixture prepared with a wettable powder ofthe active ingredient. Infection was naturally. The following resultsare obtained:

    ______________________________________                                                                  % action                                            Exp.  g of a.i. per ha    found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIF I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     25      --            32                                                2     50                    63                                                3     --      750           38                                                4     25      750      1:30 75      58     1.3                                5     50      750      1:15 88      77     1.1                                ______________________________________                                    

EXAMPLE B2

Action against Alternaria solani in tomatoes in the open (experimentalsite: Cikampek, Java, Indonesia

Tomato plants on a 7 m² plot are sprayed at 7-day intervals with a spraymixture prepared with a wettable powder of the active ingredient; intotal 9 times. Infection is naturally. For evaluation, the leaf areainfested with the fungus is measured. The following results areobtained:

    ______________________________________                                                                  % action                                            Exp.  g of a.i. per ha    found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIF I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     2.5     --            32                                                2     --      12.5          30                                                3             25            51                                                4     2.5     12.5     1:5  79      53     1.5                                5     2.5     25       1:10 80      67     1.2                                ______________________________________                                    

Similarly good results are obtained using mixtures of one of thecompounds IA, IB or IC with the compound IIF.

C) Examples in which

Component I: Compound ID (thiomethyl benzothiadiazole-7-carboxylate)

Component II: Compound IIG (metalaxyl)

EXAMPLE C1

Action against Phytophthora infestans in tomatoes

Tomato plants cv. "Roter Gnom" are sprayed to drip point with a spraymixture prepared with the formulated active ingredient, or combinationof active ingredients. After 4 days, the treated plants are sprayed witha sporangia suspension of the fungus and subsequently incubated in acabinet for 2 days at 18-20° C. and a relative atmospheric humidity of90-100%. 5 days post-infection, the fungus infestation is assessed. Thefollowing results are obtained:

    ______________________________________                                                                  % action                                            Exp.  mg of a.i. per liter                                                                              found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIG I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     5                     14                                                2     25                    36                                                3     100                   61                                                4     500                   72                                                5     --        0.1         13                                                6              1            23                                                7             10            35                                                8             50            68                                                9     5         0.1    50:1 50      25     2.0                                10    5        1       5:1  62      34     1.8                                11    5       10       1:2  87      44     2.0                                12    5       50        1:10                                                                              84      73     1.2                                13    25      50       1:2  92      80     1.2                                14    100     10       10:1 85      75     1.1                                15    100     50       2:1  95      88     1.1                                16    500     10       50:1 97      82     1.2                                ______________________________________                                    

Similarly good results are obtained with mixtures of one of thecompounds IA, IB or IC with the compound IIG. Particularly good resultswith regard to the degradability of the active ingredient in the soilare achieved by mixtures of compound ID with compound IIH.

D) Examples in which

Component I: Compound IA=benzothiadiazole-7-carboxylic acid

Component II: Compound IIG (metalaxyl)

EXAMPLE D1

Action against Phytophthora infestants in tomatoes

The experiments are carried out as described for Example C1. Thefollowing results are obtained:

    ______________________________________                                                                  % action                                            Exp.  mg of a.i. per liter                                                                              found   calculated                                                                           FS                                   No.   a.i. IA a.i. IIG I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     0.1                    0                                                2     0.5                    9                                                3     1                     22                                                4     5                     45                                                5             1             13                                                6             10            33                                                7             50            63                                                8             100           83                                                9     0.1     1         1:10                                                                              36      13     2.8                                10    0.5     1        1:2  29      21     1.4                                11    1       1        1:1  57      32     1.8                                12    1       10        1:10                                                                              79      48     1.6                                13    5       1        5:1  61      52     1.2                                ______________________________________                                    

EXAMPLE D2

Action against Pseudoperonospora cubensis in cucumbers

16-19-day-old cucumber plants ("Wisconsin") are sprayed to drip pointwith a spray mixture prepared with the formulated active ingredient, orcombination of active ingredient, or combination of active ingredients.After 4 days, the treated plants are infected with sporangia ofPseudoperonospora cubensis (strain 365, Ciba; max. 5000 per ml), and thetreated plants are subsequently incubated for 1-2 days at 18-20° C. anda relative atmospheric humidity of 70-90%. 10 days post-infection, thefungus infestation is assessed and compared with the infestation onuntreated plants. The following results are obtained:

    ______________________________________                                                                   % action                                           Exp.  mg of a.i. per liter found  calculated                                                                           FS                                   No.   a.i. IA a.i. IIG                                                                              I:II   O      E      O/E                                ______________________________________                                        0     --      --              0                                                                            (control)                                        1     0.05                    0                                               2     0.5                     6                                               3     5                      66                                               4             0.5            31                                               5             5              66                                               6             50             91                                               7     0.05    0.5     1:10   66     31     2.1                                8     0.05    5        1:100 83     66     1.3                                9     0.5     0.5     1:1    83     35     2.4                                10    0.5     5       1:10   83     68     1.2                                ______________________________________                                    

E) Examples in which

Component 1: Compound ID (thiomethyl benzothiadiazole-7-carboxylate)

Component II: Compound IIJ (pyroquilon)

EXAMPLE E1

Action against Pyricularia oryzae in rice in the open (experimentalsite: Ono, Japan)

On a 12 m² plot, rice plants are sprayed with a spray mixture preparedwith a wettable powder of the active ingredient. Infection is naturally.For evaluation, the leaf area infested with the fungus is measured 44days post-application. The following results are obtained:

    ______________________________________                                                                  % action                                            Exp.  kg of a.i. per ha   found   calculated                                                                           FS                                   No.   a.i. ID a.i. IIJ I:II O       E      O/E                                ______________________________________                                        --    --      --             0                                                                            (control)                                         1     0.25                  22                                                2     0.5                   50                                                3             0.75          46                                                4             1.5           82                                                5     0.25    0.75     1:3  80      58     1.4                                6     0.5     0.75     1:1.5                                                                              85      73     1.2                                ______________________________________                                    

Similarly good results are obtained with mixtures of one of thecompounds IA, IB or IC with compound IIJ.

F) Examples in which

Component I: Compound IA (benzothiadiazole-7-carboxylic acid)

Component II: Compound IID (fenpropimorph)

EXAMPLE F1

Action against Cercospora nicotianae in tobacco plants

6-week-old tobacco plants (cv. "Burley") are sprayed to drip point witha spray mixture prepared with the formulated active ingredient, orcombination of active ingredients. After 4 days, the treated plants areinfected with a spore suspension of Cercospora nicotianae (Ciba No. 295;max. 150,000 per ml), and the treated plants are subsequently incubatedfor 5 days at 20-22° C. and a relative atmospheric humidity of 70-90%.10 days post-infection, the fungus infestation is assessed and comparedwith the infestation on untreated plants. The following results areobtained:

    ______________________________________                                                                  % action                                            Exp.  kg of a.i. per ha   found   calculated                                                                           FS                                   No.   a.i. IA a.i. IID I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     0.2                    0                                                2     0.6                    3                                                3     2                     69                                                4     6                     79                                                5             2             13                                                6             6             23                                                7             10            42                                                8     0.2     2        1:10 52      13     4                                  9     0.2     6        1:30 61      23     2.7                                10    0.6     2        1:3  71      16     4.4                                11    6       6        1:1  100     83     1.2                                ______________________________________                                    

G) Examples in which

Component I: Compound IA (benzothiadiazole-7-carboxylic acid)

Component II: Compound IIE (fenpropidine)

EXAMPLE G1

Action against Puccinia recondita in wheat

The experiments are carried out as described for Example A1. Thefollowing results are obtained:

    ______________________________________                                                                  % action                                            Exp.  kg of a.i. per ha   found   calculated                                                                           FS                                   No.   a.i. IA a.i. IIE I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     6                     20                                                2     20                    40                                                3             20            40                                                4             60            60                                                5     6       20       1:3  73      52     1.4                                6     6       60       1:10 75      68     1.1                                ______________________________________                                    

H) Examples in which

Component I: Compound IA (benzothiadiazole-7-carboxylic acid)

Component II: Compound IIB (difenoconazole)

EXAMPLE H1

Action against Cercospora nicotianae in tobacco plants

The experiments are carried out as described for Example F1. Thefollowing results are obtained:

    ______________________________________                                                                  % action                                            Exp.  kg of a.i. per ha   found   calculated                                                                           FS                                   No.   a.i. IA a.i. IIB I:II O       E      O/E                                ______________________________________                                        0     --      --             0                                                                            (control)                                         1     2                     69                                                2     6                     79                                                3     20                    100                                               4             0.6            3                                                5             2             23                                                6             6             32                                                7     2       0.6       3:1 90      70     1.3                                8     6       0.6      10:1 100     80     1.3                                ______________________________________                                    

What is claimed is:
 1. A composition which comprises a pesticidallyeffective amount of at least two, synergistically active componentstogether with a suitable carrier material, wherein component I is acompound having a plant-immunizing action of the formula I ##STR3## andcomponent II is (RS)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alaninemethyl ester or(R)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methylester.
 2. A composition of claim 1 wherein the weight ratio of I:II is1:10 to 50:1.
 3. A composition of claim 2 wherein the weight ratio is1:2 to 50:1.
 4. A composition of claim 1 wherein --C₁ -C₄ alkyl ismethyl.
 5. A composition of claim 1 wherein component II is(RS)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester.
 6. Acomposition of claim 1 wherein component II is(R)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester.
 7. Amethod of protecting plants against plant diseases by treating theplants, parts of the plants, or their environment with a synergisticallyeffective amount of a component I and a component II in any order orsimultaneously, wherein component I is of the formula I ##STR4## andcomponent II is (RS)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alaninemethyl ester or(R)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methylester.
 8. A method of claim 7 wherein the weight ratio of I:II is 1:10to 50:1.
 9. A method of claim 7 wherein the weight ratio of I:II is 1:2to 50:1.
 10. A method of claim 7 wherein --C₁ -C₄ alkyl is methyl.
 11. Amethod of claim 7 wherein component II is(RS)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester.
 12. Amethod of claim 7 wherein component II is(R)-N-(2,6-dimethylphenyl-N-(methoxyacetyl)alanine methyl ester.